Method for manufacturing basalt fiber

ABSTRACT

Basalt filament is manufactured such that the fiber diameter can be controlled and the filament is not severed during winding. A network former and a glass modifier are formed and maintained with respect to basalt rock ore, and the crystallization and binding of basalt fiber are inhibited, the heat-resistance property of basalt fiber is greatly improved from the conventional 750° C. to 850 or 900° C., and significant cost reduction is achieved over conventional products. The method includes: grinding basalt rock as a material; washing a resultant ground rock; melting the ground rock that has been washed; transforming a molten product into fiber; and drawing the fiber in an aligned manner, and winding it. The temperature of the molten product in the melting step is 1400 to 1650° C., and log η is 2.15 to 2.35 dPa·s and preferably 2.2 to 2.3 dPa·s, where η is the viscosity of the molten product.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for manufacturing basalt fiberthat has superior sound-absorbing and heat-resistance properties, amanufactured basalt filament, and an apparatus for manufacturing basaltfilament. More specifically, the invention relates to inexpensiveheat-resistant basalt filament having superior sound-absorbing andheat-resistance properties that can be suitably used for automobilemufflers and the like.

2. Background Art

Automobile mufflers are components for absorbing exhaust noise. Theycurrently employ glass fiber as a sound-absorbing material. As a resultof the recent trend toward measures for saving more and more energy inautomobile engines and increasingly stringent exhaust gas emissionregulations, engine temperature has become higher. This has resulted inthe exhaust gas temperature of 800° C. or higher at the muffler. Thus,there is an acute need to provide the sound-absorbing material inmufflers with higher heat-resistance property (to cope with temperaturesof 850 to 900° C.).

In an example of the manufacture of heat-resistant glass fiber, E glassfiber is treated with an acid. Specifically, conventional E glass fiberhaving the composition of 50 to 63 wt. % of SiO₂, 12 to 16 wt. % ofAl₂O₃, 8 to 13 wt. % of B₂O₃, 15 to 20 wt. % of CaO+MgO, and traceamounts of Na₂O+K₂O is subjected to an immersion treatment using, e.g.,9 to 12 wt. % concentration of hydrochloric acid at 40 to 70° C. forapproximately 30 minutes to several hours. This results in the formationof silica glass in the surface layer portion having a SiO₂ content ofnot less than 80 percent by weight; thus providing the fiber withheat-resistance property.

The acid-treated E glass fiber is advantageous in that it can be easilyand cheaply spun due to the large difference between its spinningtemperature and liquid-phase temperature. However, as a sound-absorbingmaterial for the mufflers where the exhaust gas temperature can run ashigh as 700° C. or higher, the heat-resistance property of the fiber isnot sufficient and impractical. While S glass fiber has highheat-resistance property and could be used as sound-absorbing material,it is very expensive.

JP Patent Publication (Kokai) No. 2001-206733 A discloses aheat-resistant glass fiber suitable for use in the automobile mufflerswhere the exhaust gas temperature reaches 800° C. or higher. The glassfiber has a glass composition containing, for the fiber as a whole andin substantial percentage by weight terms, 56 to 58.5% of SiO₂, 12 to17% of Al₂O₃, 16 to 27% of CaO, 1 to 9% of MgO, 0 to 1% of Na₂O, and 0to 1% of K₂O, and not containing B₂O₃ nor F₂, where the surface layerportion is formed of silica glass containing 90 wt. % or more of SiO₂.The patent document also discloses a heat-resistant glass fiber obtainedby subjecting the surface of the glass fiber of the aforementionedcomposition to an acid treatment with mineral acid.

Meanwhile, basalt fiber, which is made from naturally occurring basaltore, is very inexpensive as compared with conventional glass filament.However, when it is used at high temperatures of approximately 750° C.to 900° C., crystalline phase develops from the glass component,resulting in the disappearance of flexibility, peeling at the interfacebetween the crystalline layer and the glass layer, and other problems.

Specifically, these problems are:

(1) Commercially available glass fiber that consists primarily of SiO₂,Al₂O₃, and CaO, suffers from sound-absorbing and durability propertiesproblems when exposed to high-temperature (approximately 800° C.) gas inthe exhaust system.

(2) Commercially available glass fiber that consists primarily of SiO₂,Al₂O₃, and MgO suffers from the sound-absorbing and durabilityproperties problems when exposed to high-temperature (approximately 830°C.) gas in the exhaust system.

(3) Commercially available glass filament is expensive.

(4) Application of basalt fiber using naturally occurring material isbeing considered to solve the above problems (1) to (3). Typicalexamples are the two kinds of basalt fiber that are compositionallystable and available in large quantities, namely an ore having a largeramount of SiO₂ (A, for high-temperature applications) and an ore havinga smaller amount of SiO₂ (B, for intermediate-temperature applications),both of which have approximately the same amount of Al₂O₃. Although oreA can be spun into fiber, the resultant basalt fiber has heat-resistanceproblem at temperature ranges exceeding 750° C. Ore B, on the otherhand, is associated with higher energy cost for mass production offiber.

(5) Thus, no sound-absorbing glass fiber or heat-insulating componentmaterial for automotive applications that satisfies the requirements forheat resistance, low cost, and high durability has been available.

JP Patent Publication (Kokai) No. 2001-315588 A discloses an inventionwhereby basalt fiber is added in a resin for automobile interiormaterial.

SUMMARY OF THE INVENTION

Researches conducted by the inventors have revealed that theaforementioned problems, which are caused by the use, of basalt filamentmade from naturally occurring basalt ore, are due to the followingcauses.

(1) Partial crystallization of a perfect glass phase develops, and thedevelopment of a Ca—Si—O low-melting point crystal phase causes thefibers to be bound with one another, resulting in solidification andloss of flexibility, with the apparent fiber diameter having increasedover the diameter of single fiber by several folds.

(2) A perfect glass phase is completely transformed into a crystallinephase, resulting in loss of flexibility.

(3) Commercially available glass fiber is manufactured by mixing oxidematerials including a glass network former and a network modifier to apredetermined composition and melting the mixture at high temperature,resulting in high manufacturing “cost due to the high material cost, theneed for the powder-mixing process, and” the high material-meltingtemperature.

(4) Basalt fiber is made from a natural material and therefore itsmanufacturing cost is lower than that of commercially available glassfiber. While ore B for intermediate temperature has less SiO₂ and itsviscosity in a high-temperature molten material is low, thereby allowingthe manufacture of filament having a fiber diameter of 20 mμ or less,the glass phase crystallizes at temperature of 750° C. or higher, whichmakes the material inferior in terms of heat-resistance property. On theother hand, ore A for high temperature can maintain its glass phase athigh temperature, although crystallization develops at approximately850° C., and it has high heat-resistance property. However, it has highviscosity at high temperature, which makes it necessary to increase themelting temperature for mass production, resulting in an increase inenergy cost.

Therefore, it is necessary to form and maintain a network former and aglass modifier using basalt ore, prevent the crystallization and bindingof basalt fiber, and significantly increase the heat-resistance propertyof basalt fiber from the conventional 750° C. to 850 or 900° C., as wellas achieving a significant cost reduction over conventional products.

It is therefore an object of the invention to solve the aforementionedproblems and establish a method for manufacturing basalt filament usingthe basalt material.

The invention is based on the inventors' realization that basaltfilament having superior heat-resistance property can be manufactured byselecting the melting condition of basalt ore. The inventors have alsorealized that the crystallization and binding of basalt fiber can beinhibited and a significantly improved heat-resistance property can beachieved by selecting the oxide for the network former and the glassmodifier with respect to basalt ore and optimizing their amounts added.

In one aspect, the invention provides a method for manufacturing basaltfilament, comprising the steps of: grinding basalt rock as a material;washing a resultant ground rock; melting the ground rock that has beenwashed; transforming a molten product into fiber; and drawing the fiberin an aligned manner, and winding it. The temperature of the moltenproduct in the melting step is 1400 to 1650° C., and log η is 2.15 to2.35 dPa·s and more preferably 2.2 to 2.3 dPa·s, where η is theviscosity of the molten product.

The melting conditions in accordance with the invention make it possibleto control the fiber diameter and manufacture basalt filament that isnot severed during the drawing/aligning and winding steps.

As described above; the temperature of the molten product in the meltingstep is 1430 to 1610° C. Preferably, the temperature is 1530 to 1550° C.

In the method for manufacturing basalt filament according to one ofabove-mentioned technical solutions, the basalt rock material isselected from: (1) high-temperature ore (A) having substantially thesame amount of Al₂O₃ and a larger amount of SiO₂; (2)intermediate-temperature ore (B) having substantially the same amount ofAl₂O₃ and a smaller amount of SiO₂; and (3) a mixture of thehigh-temperature basalt rock ore (A) and the intermediate-temperaturebasalt rock ore (B).

Preferably, one or more kinds of oxide selected from Al₂O₃, SiO₂, CaO,and MgO is added to the basalt rock material. Optimum amounts of theoxide added are as follows:

(1) Addition of the oxide is based on one component, of which the amountadded, via external addition, is 1.0 to 40 wt. % and preferably 10 to 30wt. % with respect to 100 wt. % of the basalt rock.(2) The oxide is based on two components of which the sum of the amountsadded, via external addition, is 1.0 to 70 wt. % and preferably 10 to 60wt. % with respect to 100 wt. % of the basalt rock.(3) The oxide is based on three or more components of which the sum ofthe amounts added, via external addition, is 1.0 to 60 wt. % andpreferably 10 to 50 wt. % with respect to 100 wt. % of the basalt rock.

In the step of transforming the molten product into fiber, the fiberdiameter can be adjusted by controlling the rate at which the moltenproduct, which is completely melted at a predetermined temperature andwhich is dropped through an opening provided at the bottom of a platinumbush, is transformed into fiber and wound.

In a second aspect, the invention provides basalt filament manufacturedby the above method.

In a third aspect, the invention provides a heat-resistantsound-absorbing material comprising the aforementioned basalt filament.

In a fourth aspect, the invention provides a muffler comprising theaforementioned basalt filament as a heat-resistant sound-absorbingmaterial.

In a fifth aspect, the invention provides an apparatus for manufacturingbasalt filament from basalt rock material, comprising: a hopper forfeeding a material that is obtained by grinding the basalt rock andwashing a resultant ground product; a furnace for melting the washedproduct with a heating means; a platinum bush comprising a number ofopenings in a lower portion thereof through which the molten product istransformed into fiber; and a winder for drawing the fiber in an alignedmanner and winding it thereon.

The melting conditions in accordance with the invention allow the fiberdiameter to be controlled and make it possible to manufacture basaltfilament that is not severed during the winding step.

Furthermore, in accordance with the invention, the crystallization andbinding of basalt fiber can be inhibited and heat-resistance propertycan be greatly improved by properly selecting the oxide for a networkformer and a glass modifier and optimizing the amount thereof added withrespect to basalt ore, and using two kinds of basalt rock ore containingdifferent amounts of elements, namely, a high-temperature ore (A)containing substantially the same amount of Al₂O₃ and a larger amount ofSiO₂, and an intermediate-temperature ore (B) containing a smalleramount of SiO₂.

Basalt rock (basalt ore) as a material for the basalt fiber according tothe invention is a kind of igneous rock. Major examples of theconstituent mineral include: (1) plagioclase: Na(AlSi₃O₈)—Ca(Al₂SiO₈);(2) pyroxene: (Ca, Mg, Fe²⁺, Fe³⁺, Al, Ti)₂[(Si, Al)₂O₆]; and (3)olivine: (Fe, Mg)₂SiO₄. Ukrainian products are inexpensive andgood-quality.

Tables 1 and 2 show examples of element ratios (wt. %) and theoxide-equivalent composition ratios (wt. %) determined by ICP analysis(using an inductively-coupled plasma spectrometer ICPV-8100 by ShimadzuCorporation) performed on a high-temperature basalt ore (forhigh-temperature applications), an intermediate-temperature basalt ore(for intermediate-temperature applications), and a glass consisting of85% high-temperature ore and 15% intermediate-temperature ore.

TABLE 1 Ore Ore (for Ore (for high-temp.) 85 wt % (for high-temp.)intermediate-temp.) Ore (for intermediate-temp.) (wt %) (wt %) 15 wt %(wt %) Si 23.5~28.8 23.5~28.5 25.0~28.8 Al 8.7~9.3 8.7~9.3 9.0~9.5 Fe6.0~6.6 6.0~7.1 5.7~6.7 Ca 4.0~4.5 5.6~6.1 4.2~4.7 Na 2.1~2.3 1.8~2.02.0~2.3 K 1.4~1.8 1.2~1.5 1.4~1.9 Mg 0.1~1.6 1.4~3.0 1.5~1.7 Ti 0.4~0.60.5~0.7 0.4~0.6 Mn 0.1~0.2 0.1~0.2 0.1~0.2 P 0.05~0.10 0.05~0.090.07~0.10 B 0.02~0.08 0.01~0.06 0.03~0.10 Ba 0.03~0.05 0.03~0.05 0.09 Sr0.02~0.04 0.02~0.04 0.02~0.05 Zr 0.01~0.04 0.01~0.04 0.01~0.03 Cr0.01~0.03 0.01~0.03 0.01~0.03 S 0.01~0.03 0.01~0.03 0.01~0.03

TABLE 2 Ore (for high-temp.) Ore Ore (for 85 wt % Ore (for (forhigh-temp.) intermediate-temp.) intermediate-temp.) (wt %) (wt %) 15 wt% (wt %) SiO₂ 57.1~61.2 54.0~58.2 57.7~60.6 Al₂O₃ 16.1~19.2 14.9~18.116.5~18.9 FeO + Fe₂O₃ 8.0~9.7 8.1~9.6 7.7~9.6 CaO 5.5~6.8 7.5~8.85.8~7.0 Na₂O 2.8~3.3 2.2~2.9 2.6~3.2 K₂O 1.8~2.1 1.4~1.8 1.8~2.2 MgO0.20~2.5  1.4~4.8 0.2~2.8 TiO₂ 0.7~1.0 0.8~1.1 0.1~0.3 MnO 0.1~0.30.1~0.3 0.1~0.3 P₂O₅ 0.1~0.3 0.1~0.3 0.1~0.3 B₂O₃ 0.1~0.3 0.04~0.200.04~0.30 BaO 0.03~0.07 0.02~0.06 0.03~0.12 SrO 0.02~0.06 0.02~0.070.01~0.06 ZrO₂ 0.02~0.05 0.02~0.05 0.01~0.30 Cr₂O₃ 0.01~0.05 0.01~0.050.01~0.04 SO 0.01~0.03 0.01~0.03 0.01~0.03

FIG. 1 shows the outline of the steps involved in the manufacture ofbasalt filament according to the invention. As shown in FIG. 1, thematerial basalt rock is ground into a predetermined grain size. Theresultant ground rock is washed and thrown into a material-feedinghopper of a furnace. The furnace is a gas and/or electric furnace thatis surrounded with heat-insulating furnace material. The raw material isheated with a burner via the surface thereof so as to melt it. Themolten material passes through a platinum bush having a number ofopenings at the bottom thereof, whereby the material is transformed intofiber. The fibrous basalt is drawn in an aligned manner by a fiberwinding machine and wound thereon.

FIG. 1 also schematically shows a basalt filament manufacturingapparatus used in accordance with the invention. The furnace of theapparatus is characterized in that: (1) it is an independent furnace;(2) each furnace is provided with one bushing; (3) it is based on abatch-furnace concept so as to carry out the procedure involving thebasalt rock feeding opening, furnace, bushing, and windingindependently. The apparatus has the following advantages:

(1) The furnace can be repaired by partially ceasing production. Forexample, when there are a plurality of furnaces, they can be repairedregularly while production is maintained.

(2) The apparatus can handle small-lot production, and is also capableof production using different materials.

The basalt rock material is rendered into a completely molten productusing the electric or gas furnace at a predetermined temperature. Themolten product is drawn via the bottom of the platinum bush at apredetermined rate so as to produce filaments having a filament diameteron the order of several μm to several dozens of μm. For application assound-absorbing material in particular, the diameter is preferably 15 to20 μm. The fiber diameter of basalt filament can be controlled by avariety of factors, such as the composition of the molten product, thetemperature of the molten product, the high-temperature viscosity of themolten product at a predetermined temperature, and the size, shape, andposition of the openings provided in the bottom of the platinum bush.Another important factor involves the control of the pulling forceduring the step of obtaining fiber. Normally, this is controlled by therate at which the fiber is wound, namely, the rotation speed. In orderto obtain a filament, it is indispensable that the fiber is not severedduring winding. Thus, it is also important to optimize the factors thatdetermine the fiber diameter, including the factor that prevents thebreakage of fiber. Thus, in accordance with the invention, it isimportant to obtain a filament without severing the fiber having adiameter of several dozens of μm.

In the method for manufacturing basalt rock filament using basalt rockmaterial, it is important to adjust the temperature and viscosity of amolten product. It is indispensable that the viscosity of the moltenproduct at high temperature is measured accurately and that the methodis controlled such that an optimum viscosity can be obtained dependingon the composition of the material. Herein, the viscosity of glass ismeasured (a sample pull-down method) in order to evaluate thehigh-temperature viscosity of a molten product. The principle of thesample pull-down method is based on the fact that, when a Pt spheremoves with constant velocity in a glass molten body, the viscosity isdetermined by Stokes' law as follows:

η=GW/ν

where G is apparatus constant, W is load, and ν is the rate at which thePt crucible is pulled down.

In the following, an embodiment of the invention will be described.

EMBODIMENT

Using the filament manufacturing apparatus shown in FIG. 1, filamentswere manufactured using a variety of basalt rock materials. The basaltrocks used include: (1) high-temperature basalt rock (A); (2)intermediate-temperature basalt rock (B); (3) basalt rock materialconsisting of high-temperature basalt rock (A) to which a one-componentsystem, two-component system, and a three-component system oxide wereadded; (4) a mixed basalt rock material consisting of high-temperaturebasalt rock (A) and intermediate-temperature basalt rock (B); and (5) amaterial consisting of a mixed basalt rock of high-temperature basaltrock (A) and intermediate-temperature basalt rock (B) to which anotheroxide was added. These materials were fed through the hopper and meltedin the gas furnace whose temperature was maintained at a predeterminedlevel. The size of basalt rock may be on the order of several mm toseveral dozens of mm, or several μm to several dozens of mm. Thematerial feeding rate and the amount of fiber taken out of the platinumbush must be maintained at constant levels so that the liquid level ofthe molten product can be constant. Various compositions may be adoptedfor the heat-shielding furnace material. It is necessary, however, thatthe material does not become corroded too much by the reaction with themolten product or by the molten product. When a mixed material is used,necessary materials may be mixed in advance, or they may be fedseparately using a plurality of hoppers such that a predeterminedcomposition is achieved. Observation of the exterior and shape of theresultant fiber showed that a transparent filament with brownish tinthad been obtained.

The melting conditions in accordance with the invention allow the fiberdiameter to be controlled and, in addition, make it possible tomanufacture basalt filament that is not severed during thedrawing/aligning and winding steps. Furthermore, in accordance with theinvention, the crystallization and binding of basalt fibers can beinhibited, and the heat-resistance property can be significantlyimproved. As a result, the invention can provide a heat-resistantsound-absorbing material suitable for mufflers and the like at low cost.

1-9. (canceled)
 10. Basalt filament manufactured by a method formanufacturing, comprising the steps of: grinding basalt rock as amaterial; washing a resultant ground rock; melting the ground rock thathas been washed; transforming a molten product into fiber; and drawingthe fiber in an aligned manner, and winding it, wherein the temperatureof the molten product in the melting step is 1400 to 1650° C., andwherein log η is 2.15 to 2.35 dPa·s, where η is the viscosity of themolten product, wherein the basalt rock material comprises a mixture ofa high-temperature basalt rock ore and an intermediate-temperaturebasalt rock ore, an amount of Al₂O₃ in the high-temperature basalt rockore is substantially the same as an amount of Al₂O₃ in theintermediate-temperature basalt rock ore, and an amount of SiO₂ in thehigh-temperature basalt rock ore is larger than an amount of SiO₂ in theintermediate-temperature basalt rock ore.
 11. The basalt filamentaccording to claim 10, wherein, in the method for manufacturing basaltfilament, the temperature of the molten product in the melting step is1530 to 1550° C.
 12. The basalt filament according to claim 10, wherein,in the method for manufacturing basalt filament, one or more kinds ofoxide selected from Al₂O₃, SiO₂, CaO, and MgO is added to the basaltrock material.
 13. The basalt filament according to claim 10, wherein,in the step of transforming the molten product into fiber in the methodfor manufacturing basalt filament, the fiber diameter is adjusted bycontrolling the rate at which the molten product, which is completelymelted at a predetermined temperature and which is dropped through anopening provided at the bottom of a platinum bush, is transformed intofiber and wound.
 14. A heat-resistant sound-absorbing materialcomprising the basalt filament according to claim
 10. 15. A mufflercomprising the basalt filament according to claim 10 as a heat-resistantsound-absorbing material.